Nickel-rhenium hydrogenation catalyst and methods of preparing same and using same

ABSTRACT

The present invention concerns a new nickel-rhenium catalyst and method of preparing said catalyst. The invention also relates to the catalytic amination of lower aliphatic alkane derivatives such as alkanemono-ols, alkanediols and alcoholamines utilizing the new nickel-rhenium catalyst.

This application is a division of our prior U.S. application: Ser. No.647,065 Filing Date Jan. 7, 1976.

BACKGROUND OF THE INVENTION

A considerable number of methods for production of alkylamine productshave been proposed and a number of them have been commercially utilized.The present invention particularly concerns the production of loweralkylamines and alkyldiamines by the catalytic amination of loweraliphatic alkane derivatives including mono- and polyhydric alcohols,alcoholamines, and compounds from which these alcohols are derived,including alkoxides, ketones and alkyleneimines.

The catalytic amination of alcohols is a process which has been longrecognized in the prior art. It generally concerns the reaction ofalcohol with ammonia in the presence of a hydrogenation catalyst andusually in the presence of hydrogen.

The most difficult problem in the manufacture of amines by this andother proposed processes is that the chemical synthesis reactions usedalso form substantial amounts of byproducts, which are of considerablyless value and as a result often render the synthesis inefficient andnot commercially feasible.

The most desirable amine products generally are those products whereinan amine group replaces the non-amine functional group or groups in thealkyl starting material without any further modification of the startingmaterial. Most heavier, more highly substituted amines and heterocyclicnitrogen compounds can be further synthesized from these preferredalkylamines and diamines. A synthesis of these heavier, substituted, andheterocyclic amines directly from the alkyl starting materials usuallyyields other unwanted by-products.

The amine products produced in accordance with the present inventionhave many uses. In addition to their use as intermediates forsynthesizing other chemical materials, they are utilized in fungicidesand insecticides.

For convenience in the description of the invention hereinbelow, theamination of ethylene glycol and monoethanol amine to ethylenediamineand other products will be most comprehensively discussed, although thepresent invention is not limited to these starting materials.

The amination of ethylene glycol may be illustrated by the followingchemical formula with the primary products being monoethanolamine (MEA),ethylenediamine (EDA), and piperazine (also termed diethylenediamine,DEDA): ##STR1##

Numerous other chemical reactions are known for producing alkylaminesand diamines. For example, in the synthesis of ethylenediamine, thefollowing reactions have been proposed: the hydrolysis of ethylene urea;reductive amination of formaldehyde cyanohydrin; the reduction ofcyanogen; the reduction of 1,2-dinitroethane; and the amination ofchloroacetylchloride followed by reduction. None of these chemicalprocesses appear to have been operated on a commercial scale because ofthe process requirements and costs of raw materials.

One of the most widely used commercial processes for producingethylenediamine today involves a reaction of ethylenedichloride withaqueous ammonia. The ethylenedichloride is reacted with aqueous 30 to40% ammonia to produce a dilute aqueous solution of amines. Sodiumhydroxide is then added to neutralize the hydrochloric acid formed inthe ammonia-ethylene dichloride reaction. This neutralization step formsadditional water and gives rise to by-product sodium chloride. Anillustration of the approximate distribution or profile of productsproduced by such a process is as follows:

    ______________________________________                                        Products             Wt. % of Production                                      ______________________________________                                        Ethylenediamine (EDA)                                                                              41%                                                      Diethylenetriamine (DETA)                                                                          25%                                                      Triethylenetetramine (TETA)                                                                        10%                                                      Tetraethylenepentamine (TEPA)                                                                       8%                                                      Pentaethylenehexamine (PEHA)                                                                       13%                                                      Polyamine Heavies (PAH)                                                                            13%                                                      Piperazine (DEDA)    1.5%                                                     Aminoethylpiperazine (AEP)                                                                         1.5%                                                     ______________________________________                                    

About 2.5 lbs. of sodium chloride is produced per lb. of the aminesproduced.

Although the product distribution is commercially feasible, the presenceof chlorine in the system, including in the corrosive form of hydrogenchloride, causes expensive maintenance costs. Moreover, recovery of thedesired amine products from the salt-containing aqueous solution isdifficult and the disposal of the large quantities of salt is an everincreasing environmental problem. The cost of the starting materialsalso has been a discouraging factor.

A method which has recently emerged commercially is the reduction ofamino acetonitrile to form ethylenediamine. Although this process,according to the literature can be operated to produce as much as 90%ethylenediamine in the amine yield, the expense of the startingmaterials in the process and other economic considerations do not makethis process commercially attractive.

As indicated above, the catalytic amination of alkane derivativesincluding aliphatic alcohols and aminoalcohols has been the subject ofmuch investigation and prior art literature. The applicant has nowdiscovered a new catalyst which is both more active and more selectivethan previously known catalysts for carrying out amination processes. Itshould be noted that there are numerous materials which have the abilityto catalyze such amination processes, but the mere ability to catalyzeis far from sufficient to accord a catalyst one of commercialsignificance.

U.S. Pat. No. 2,861,995 describes a method of converting ethanolamine tovarious nitrogen-containing products by using a metal hydrogenationcatalyst comprising one or more of nickel, cobalt, copper chromite,catalytic noble metals such as platinum and palladium, and Raney nickeland Raney cobalt. They may be supported on a carrier such as alumina.

U.S. Pat. No. 3,068,290 describes a process for converting ethanolamineto ethylenediamine by using a hydrogenation catalyst, such as describedabove, in a reaction which is in the liquid phase, under autogenouspressure. The patent also describes a preferred catalyst which is acombination of nickel and magnesium oxides (Ni-MgO), obtained by thermaldecomposition of coprecipitated nickel and magnesium formates oroxalates.

U.S. Pat. No. 3,137,730 teaches the conversion of ethylene glycol byusing a supported catalyst comprising nickel and copper. U.S. Pat. No.3,270,059 teaches an amination process in the presence of a supportedcatalyst which is produced by sintering oxygen compounds of eithernickel or cobalt at temperatures in excess of 700° C and reducing thesintered metal compound by treatment with hydrogen. U.S. Pat. No.3,766,184 describes a catalyst containing iron with either nickel,cobalt or mixtures thereof. Ruthenium catalysts are also referred to inthis and other patents as useful in amination processes.

None of the catalysts heretofore known have been commercially successfulbecause of one or more inadequacies. Modern commercial catalyticprocesses require catalysts to be more than active, i.e., yield highconversions in the chemical reactions they catalyze. In the case ofamination processes where numerous competing reactions occur yieldingmany by-products, it is important for the catalyst to have goodselectivity or the ability to afford a high yield of useful product witha concomitant small yield of undesired product. The optimum reactionconditions including temperature, pressure and relative proportions ofreactants, as well as reaction time, may be determined by the catalyst,and in so doing may affect the economics of the whole process. The costof the catalyst, its method of preparation and its effective life aswell as its physical properties may be determinative of a successful,viable process.

The applicant has now discovered a new catalyst containing nickel andrhenium, supported on a material selected from α-aluminas, silica,silica-aluminas, kieselguhrs and diatomaceous earths which have improvedproperties over those catalysts heretofore known for catalyzing theamination of aliphatic lower alkyl derivatives.

SUMMARY OF THE INVENTION

This invention relates to a new catalyst comprising a mixture of nickeland rhenium impregnated on various support materials includingα-alumina, silica, silica-alumina, kieselguhrs and diatomaceous earthswhich are active and selective in the conversion of various alcohols todesirable amine products. It has been found that these nickel-rheniumcatalysts not only exhibit excellent conversion activity but at the sametime have superior selectivity in the production of greater amounts ofdesired amine products yet comparatively smaller quantities of lessdesired by-products.

The nickel-rhenium catalysts of this invention possess a wide spectrumin magnitude of catalytic activity; can be used in relatively smallconcentrations; permit the use of a better balance of reactants; andenables the use of reasonable reaction conditions for carrying out theprocess.

The applicant has further discovered that by controlling certainvariables both in the preparation of the catalyst and in the catalyticamination process itself, the activity and selectivity of the aminationreaction can be even further optimized and improved.

It has also been found that other metals may be present in the catalystin admixture with the nickel and rhenium.

It has additionally been discovered that the nickelrhenium catalyst ofthe present invention has surprising activity and selectivity in theamination of a wide range of compounds including, for example,alkoxides, monohydric and polyhydric alcohols, ketones, alkaneimines andaminoalcohols.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

According to the present invention there are provided new catalystshaving high activity and selectivity in the amination of alcohols toalkylamines, said catalysts comprising rhenium (atomic number 75) andnickel impregnated on a support material selected from α-aluminas,silica, silica-aluminas, kieselguhrs or diatomaceous earths, wherein themole ratio of the nickel to the rhenium is in the range of from about2:1 to about 30:1 and wherein the catalyst is activated by reduction inthe presence of hydrogen at elevated temperature.

Another feature of the present invention is a process for preparing saidnickel-rhenium catalyst, said process comprising (i) impregnating amixture of metals comprising rhenium and nickel on a support materialselected from the group consisting of α-alumina, silica, silica-alumina,kieselguhrs and diatomaceous earths; and (ii) activating said catalystby reduction by heating the catalyst in the presence of hydrogen at atemperature in the range of about 200°-600° C for a period of about 45minutes to about 4 hours.

A further feature of the present invention is a method for producinglower aminoalkanes and diaminoalkanes by the catalytic amination oflower aliphatic alkane derivatives including alkoxides, alkanemono-ols,alkanediols, alkanolamines, detones, iminoalkanes and iminoalkanols andmixtures thereof, said process comprising contacting said lower alkanederivatives with ammonia under pressure at a temperature of from 150° to350° C and in the presence of hydrogen and the nickel-rhenium catalystas described hereinabove.

The amination of alcohols involves a reaction between ammonia andalcohol in the presence of hydrogen gas. The amination process consistsof a series of hydrogenation and dehydrogenation catalytic reactions.The mechanism of these various reactions have been extensively discussedin the prior art literature and are illustrated in the seven reactionformulas below: ##STR2## The first step in the amination process isbelieved to be a reversible dehydrogenation of the alcohol to give anintermediate aldehyde [1]. The aldehyde is then converted to anaminoalcohol [2] by reaction with ammonia or an amine present in thereaction mixture. The aminoalcohol then loses water to form the imine[3]. The imine is then hydrogenated to the amine [4]. When theintermediate aldehyde or the imine react with amines in the reactionmixture, substituted and heavier amines are formed. Formulas 5, 6, and 7illustrate the possible products formed by a reaction of theintermediate imine with ammonia or amines present in the reactionmixture. The products most often present in the reaction mixture whereethylene glycol or monoethanolamine are the starting materials, include:

Ethylene Glycol (EG)

Monoethanolamine (MEA)

Ethylenediamine (EDA)

Piperazine (DEDA)

Diethylenetriamine (DETA)

Aminoethyl ethanolamine (AEEA)

Aminoethyl piperazine (AEP)

One of the major shortcomings in the previously known techniques insynthesizing the more desirable alkylamines and diamines is thesimultaneous production of substantial amounts of less desirableby-products.

The production of excessive amounts of undesirable materials means aninefficient utilization of raw materials and additional problemsincurred in separating the desired products from the reaction mixtureand disposing of the waste products. A recent analysis of the currentand forecasted demands of the pertinent nitrogen-containing productsindicates that the greatest demand is for ethylenediamine. On the otherend, there is little if any demand for piperazine (DEDA) and derivativesof piperazine like aminoethyl piperazine (AEP). As a result, theselectivity of amination catalysts to produce a favorable distributionof products is illustrated herein by comparing the amount ofethylenediamine (EDA) produced by the process with the amount ofpiperazine (DEDA) produced for a given conversion.

There has therefore been great demand for a catalyst which has theability to obtain high amination conversion rates yet maintain goodselectivity in the products produced. The nickel-rhenium catalyst of thepresent invention has been shown to have these and other advantages inthe amination of lower alkanes having one or more functional groups.

The nickel-rhenium catalysts of the present invention are solidcatalysts wherein the nickel and rhenium metals are supported on certainmaterials which have been known for use as supporting materials forother catalysts.

The support materials which have been found to produce the most activeand selective amination catalysts are those supports which are composedof silica, silica-alumina, -alumina, silica-titania, kieselguhrs anddiatomaceous earths. These support materials are well-known in the artand are commercially available.

Support materials are not equivalent in their ability to form activeNi-Re catalysts. For example, carbon supported Ni-Re catalysts such asCXC carbon from National Carbon Company, even with large surface areas,have not shown catalytic activity in amination reactions.Silica-magnesia supported Ni-Re catalysts have also not shown catalyticactivity in amination processes.

Among the aforementioned support materials which have yielded activeNi-Re catalysts, even they are not equivalent. Those supports which formmore active catalysts yield optimum amination conversions at less severereaction conditions, eg., lower reaction temperatures. Therefore,although all supports tested within the group indicated above show somecatalytic activity in the amination reactions, some supports within ageneral type have not been considered as having strong commercialpromise because more extreme reaction conditions, such as higherreaction temperatures, must be used to obtain satisfactory conversions.

The actual effectiveness of a material as a support in a Ni-Re catalystis generally not predictable in advance. However, among the generaltypes of supports indicated above that have been found active, thereappears to be some relationship between catalytic activity and theamount of surface area of the particular support materials. Among thegeneral active types of supports, it has been found that the higher thesurface area for given weight of support, the more active the Ni-Recatalyst produced.

One possible explanation for the surface area effect on catalystactivity is that a number of the reactions in the amination processoccur on the catalyst surface and are therefore affected byadsorption-desorption equilibria of the reaction materials. The activityof a nickel-rhenium catalyst would therefore be effected, within certainlimits, by varying surface area of the supports and other surfaceproperties including support shape, pore size, and pore volume.Generally, greater dispersion of the nickel and rhenium metals on highersurface area active supports produce more active Ni-Re catalysts.

Specific examples of some of the more active support materials for theNi-Re catalyst of the present invention are listed in the table below:

                  TABLE 1                                                         ______________________________________                                                                     Surface Area                                     Support        General Type  m.sup.2 /gm                                      ______________________________________                                        Girdler T869   Silica-alumina                                                                              ˜ 60                                       Girdler T1571  Silica-alumina                                                                              ˜150                                       Girdler T372   α-alumina                                                                             ˜ 40                                       Girdler T373   Silica-alumina                                                                              2-3                                              Girdler K306   Silica-alumina                                                                              ˜250                                       Girdler T2085  Silica-alumina                                                                              ˜113                                       Girdler K10    Silica-alumina                                                                              ˜268                                       Girdler T2045  Kieselguhr                                                     Norton LA 4102 α-alumina                                                                             1                                                Johns-Manville Diatomaceous  10-15                                             Type III       silica                                                        Grace 980-13   Silica alumina                                                                              375                                              Grace 980-25   Silica alumina                                                                              375                                              Laboratory     Silica titania                                                                               84                                                              (SiO.sub.2 /TiO.sub.2                                                         Mole Ratio 9:1)                                               ______________________________________                                    

In the amination reactions of the present invention, Ni-Re catalystscomprising active supports having a surface area of 1 m² /gm or greaterare preferred.

The particular size and shape of the support material has not been foundto have any appreciable effect on the catalytic properties of Ni-Recatalysts formed therefrom. The support materials which may be used inmaking the Ni-Re catalyst may be of any convenient shape or size. Theshape of the support usually will depend upon the shape required in theparticular apparatus used to perform the catalytic conversion reaction.Successful Ni-Re catalysts have been made on support materials in theform of powders, spherical pellets and extruded strips. Impregnatedspherical pellets ranging in diameter from 1/8 inch to 3/16 inch havebeen used. Extruded strips of a cylindrical-type shape ranging from 1/32inch to 1/2 inch in length have also been used as successful supportsfor Ni-Re catalysts of the present invention.

The particular method of impregnating or coating the nickel and rheniummetal onto the support material has not been found to have a significanteffect on the activity or selectivity of the final catalyst in aminationprocesses. However, the amount of metal impregnated onto the supportmaterial and the nature of the support itself, as discussed above, doesaffect or vary the catalytic activity.

One technique for impregnating the nickel and rhenium onto the supportis to use a solution of salts of the metals as a vehicle.

Various organic and inorganic nickel and rhenium salts may be used inimpregnation solutions. Examples of suitable nickel-containing salts areanhydrous and hydrated nickelous nitrate [hydrate: Ni(NO₃)₂ ·6H₂ O] andnickel acetonyl acetate [Ni(C₅ H₇ O₂)₂ ]. Suitable rhenium salts for usein the impregnating solution are ammonium perrhenate [NH₄ ReO₄ ] andrhenium paradioxane [Re₂ O₇ ·3(C₄ H₈ O₂)]. In some cases, it isadvantageous to heat the solvent liquid to bring the metal salts intosolution.

The salt solution should be prepared by considering two factors. Thefirst concerns the amount of total metal desired to be impregnated on aspecific quantity of support. The second factor concerns the relativeatom ratio of nickel to rhenium. Both factors have been found to affectthe final properties of the catalyst.

The most active catalysts have been found to be those in which the Ni/Reatom ratio is between 2:1 and 30:1. In most cases, maximum activityoccurs with a Ni/Re atom ratio between 5:1 and 20:1. Example 3 belowdemonstrates the effect varying Ni/Re atom ratio has on activity of thecatalyst. In preparing the catalyst, the Ni/Re atom ratio is obtained bepredetermining the corresponding relative proportions of the metal saltsto be present in the impregnation solution.

The total metal to be impregnated onto the support also has an effect onthe activity of the catalyst. Example 4 demonstrates that varying themetal loading has a different effect on a silica (Girdler T1571) and asilica-alumina (Girdler T869) supported catalyst. Example 4 indicatesthat the silica supported catalyst having a high surface area hadgreater activity with greater amounts of metal present. Thesilica-alumina supported catalyst, with a lower surface area than thesilica support, had greater activity with 12.5% metal on the support ascompared with 30% metal.

Ni-Re catalysts in accordance with the present invention contain a totalnickel plus rhenium metal content in the range 3-30% by weight of thesupport material. Most Ni-Re catalysts exhibit maximum activity withNi-Re contents in the range 5-15% by weight of the support.

Where relatively large amounts of metal are to be impregnated onsupports with relatively low surface areas or possibly high densities, asingle impregnation step may not be sufficient. Although an impregnationsolution may be prepared with the minimum amount of solvent required todissolve the metal salts, the total amount of the impregnation solutionmay be greater than that which the support material can absorb, orbeyond the maximum absorption amount.

In such case, a portion of the impregnation solution less than themaximum absorption amount is used to initially contact the supportmaterial. After contacting, the support material is dried and thencontacted with an additional amount of the impregnation solution. Thesequential steps of contacting with solution and drying are continueduntil all of the impregnation solution is used. A typical drying stepcan comprise heating the impregnated support to a temperature of 120° Cfor several hours. Evacuation drying may also be used, where the supportis cooled under reduced pressure.

It is also advantageous to dry the support material prior toimpregnation in order to insure that the support will take up as much ofthe solution as possible. This pre-drying step also enables the metal topermeate more deeply into the support during impregnation. Thepenetration of the metal into the support may be further increased bytechniques known to those skilled in the art such as by increasing thetime the support is in contact with the solution.

Other impregnation techniques are well known in the art and may beutilized in the present invention. Another technique which can be usedis often characterized as a "sugar coating" technique where the metal ispredominantly present on the outer surface of the support material.

This sugar coating technique differs from the impregnation processdescribed above by the addition of a precipitant at the time theimpregnating salt solution is in contact with the support material. Theprecipitant converts the metal salt solution into a slurry. Thisimpregnating vehicle reduces the penetration of the salts beyond thesurface of the support material. The slurry in contact with the supportmaterial is then evaporated to dryness leaving the metal adheringpredominantly to the support surface.

After the support material is impregnated with the desired amount ofnickel and rhenium metal, it is completely dried and then activated by areduction step.

The drying step to be used is any technique which sufficientlyevaporates the volatile constituents of the impregnating solution. Thedrying step may comprise heating the catalyst to a temperature of about120° C. The drying may be done under an inert atmosphere, such asnitrogen, and the catalyst may be cooled under reduced pressure.

In the reduction step, the atmosphere in contact with the catalyst ishydrogen which is fed over the catalyst in an elevated temperature inthe order of 300° to 600° C for periods of from about 45 minutes toabout 4 hours. The specific conditions for reduction are dependent uponthe particular catalyst composition being activated.

Prior to the reduction or activation step, the catalyst may beoptionally calcined. In a preferred calcining step, the catalyst isheated to temperatures in the range of about 300° to 500° C for 45minutes to about 3 hours or more. The calcining may be carried out underan inert atmosphere, such as under nitrogen.

The nickel-rhenium catalysts of the present invention include catalystswhich contain various other metals in admixture with the nickel andrhenium which do not detrimentally affect the catalytic properties ofcatalysts containing nickel and rhenium as the only impregnated metals.These additional metals, in certain amination processes, may actuallyimprove selectivity and activity of the basic Ni-Re catalyst. Certain ofthese metals may extend the activity life of the nickel-rheniumcatalyst. Examples of catalysts containing additional metal componentsinclude Ni-Re-Na, Ni-Re-Ca, Ni-Re-Mg, Ni-Re-Sr, Ni-Re-Li, Ni-Re-K,Ni-Re-Ba, Ni-Re-Ce, Ni-Re-La, Ni-Re-W, Ni-Re-Fe, Ni-Re-Ru, Ni-Re-Cu,Ni-Re-Ag, Ni-Re-Zn, Ni-Re-Co, Ni-Re-U, Ni-Re-Ti and Ni-Re-Mn. In orderto prepare such catalysts, salts of these additional metals are added insuitable amounts to the impregnation solution containing the nickel andrhenium salts.

As indicated above, the amination of alkane derivatives is a processwhich has been extensively investigated and is well documented in theprior art. The reaction conditions for the process to occur aregenerally known but are particularly dependent upon the activity of theamination catalyst present. When amination processes are catalyzed bythe nickel-rhenium catalyst of the present invention, the conversion andactivity of the reaction are significantly and surprisingly improved,and the reaction conditions required are generally less severe.

The alkane derivatives which may be aminated in accordance with thepresent invention include lower aliphatic alkane derivatives having oneor more functional groups. Preferred lower aliphatic alkane derivativesinclude those containing one to six carbons. The functional groupspresent may be on the primary, secondary or tertiary carbon atoms. Thepreferred functional groups include hydroxy, amino, imino groups andcombinations of said groups. Illustrative examples of preferred alkanederivative starting materials include ethanol, ethyleneglycol(ethanediol), monoethanolamine, ethyleneimine, isopropanol,propanolamines, propanediols, acetone, butanols, butanediols,aminobutanols, pentanols, pentanediols, aminopentanols, hexanols,hexanediols and aminohexanols. The starting materials contemplatedherein also include compounds from which the aforementioned may bederived. Preferably, at least one of the functional groups in thestarting material is a hydroxy group.

The particular alkane derivative starting materials to be used, ofcourse, depends upon the particular amine product desired to beproduced. Generally, the desired aminated product differs from thealkane starting material by the amine group which replaces the non-aminefunctional group or groups present in the starting material. Forexample, in the production of ethylene diamine, starting materialsinclude ethylene glycol and monoethanol amine.

In the amination process of the present invention, the alkane derivativestarting material is reacted at an elevated temperature with ammonia inthe presence of hydrogen and the nickel-rhenium catalyst. Thetemperature for the reaction depends upon the particular startingmaterial, ratios of reactants, and most importantly, the activity of thecatalyst used. Generally, in processes of the present invention,temperatures within the range of 125° to 350° C are suitable while apreferred range is 150°-225° C.

A relatively high pressure for the reaction is also preferred. Normally,the increased pressure is obtained by the desired amount of ammonia andhydrogen already present in the reaction vessel, which is then heated tothe reaction temperature. The pressure at the time of reaction shouldnormally be within the range from about 500 to about 5,000 psig andpreferably from 800 to about 4,500 psig.

The ammonia employed in the reaction may be anhydrous or may containsmall amounts of water. Any water introduced into the reaction mixturewith the ammonia should be considered when conversion of the reaction isevaluated by the presence of water in the final mixture.

Normally, the process is run in an excess of ammonia to ensure reactionswith ammonia and not an amine present in the reaction mixture. This isone means of improving the yield of the desired aliphatic alkylamineproduct. In some catalytic systems a large excess of ammonia must bepresent. One advantage of the present invention is that because of theexceptional selectivity of the nickel-rhenium catalyst of the presentinvention, only a relatively small excess of ammonia is required.

It has been found that increasing the mole ratio of ammonia to thealkane derivative reactant decreases the activity or conversion rate ofthe reaction. This occurrence may be due to the fact that excessiveamounts of ammonia will reduce the amount of available surface of thecatalyst for access by the alkane derivative reactant.

In the amination processes of the present invention, the ammonia shouldbe present in an amount at least equivalent to the stoichiometric amountrequired by the alkane derivative reactant. The ammonia shouldpreferably be present in an amount between 2 times and 30 times thestochiometric amount required.

In the production of ethylene diamine from ethyleneglycol,monoethanolamine or mixtures thereof, ammonia is preferably present inan amount to give a mole ratio of EG and/or MEA to ammonia in the range4:1 to 20:1.

The amount of hydrogen gas present in the amination process of thepresent invention is not critical. Usually, the addition of hydrogen inan amount sufficient to bring the reaction mixture to the desiredreaction pressure is sufficient.

Where selectivity is of primary concern in the amination process, it ispreferred not to run the process to a high conversion. It has been foundthat selectivity to the preferred aminoalkanes decreases as conversionincreases.

One possible explanation for why selectivity decreases as conversionincreases is that the heavier and more substituted nitrogen products areproduced as a result of a chain of consecutive reactions. For example,it has been suggested that the piperazine by-product formed in theamination of monoethanol amine is produced by either route 1, 2 or 3shown below:

    ______________________________________                                        (1)    MEA→ EDA→ AEEA→ piperazine (DEDA)                 (2)    MEA→ EDA→ piperazine (DEDA)                              (3)    2MEA→ AEEA→ piperazine (DEDA)                            ______________________________________                                    

The amination process of the present invention may be carried out in anyconventional high pressure equipment having agitating and heating means.The process may be carried out as a continuous process of by batch. Incontinuous equipment no agitating means is required as the nature of thecontinuous process causes the reactants to continually flow in intimatecontact with the catalyst material.

The amount of Ni-Re catalyst present in an amination process depends onmany variables including the reactants, the relative proportions of thereactants, reaction conditions, and the degree of conversion andselectivity desired. Moreover, the amount of catalyst will depend alsoon the nature of the catalyst itself, e.g., its metal loading andactivity. In sum, the catalyst should be present in the aminationreaction in sufficient catalytic amount to enable the desired reactionto occur.

In the examples below, some of the materials used were obtained from thefollowing sources:

Girdler supports were obtained from the Girdler Division of ChemetronCorporation, P. O. Box 337, Louisville, Ky.

Norton supports were obtained from the Catalyst Skill Center.

The Johns Manville supports were obtained from Johns-Manville ProductsCorporation, 8741 Americana Blvd., Indianapolis, Ind. 86268.

Ammonium perrhenate (NH₄ ReO₄) was obtained from Cleveland RefractoryMetals, 28850 Aurora Road, Solon, Ohio 44139.

Nickelous nitrate [Ni(NO₃)₂ ·6H₂ O] was J. T. Baker analytical reagentgrade.

Other chemicals referred to in the examples are reagent grade andcommercially available from numerous sources.

EXAMPLE 1 Analytical Method for Determining the Activity of an AminationCatalyst

In order to develop catalyst activity data, analytical methods to permitthe determination of the degree of reactant conversion and the productdistribution are required. The degree of conversion, X, is defined byequation (1); and ##EQU1## to determine X_(a) at various reaction times,knowledge of the reactant-alcohol concentration-time profile isrequired.

The activities of the various catalysts tested have been ranked bydetermining the amount of water produced under standard reactionconditions. Each mole of MEA or EG converted produces a mole (or twomoles in the case of EG) of water and the

    ______________________________________                                        NH.sub.3 + H.sub.2 NCH.sub.2 CH.sub.2 OHH.sub.2 NC.sub.2 H.sub.4 NH.sub.2     + H.sub.2 O                                                                   2NH.sub.3 + HOC.sub.2 H.sub.4 OHH.sub.2 NC.sub.2 H.sub.4 NH.sub.2 +           2H.sub.2 O                                                                    ______________________________________                                    

catalyst producing the most water is the most active. The water producedis easily determined by Karl Fischer titration of the (ammonia free)reaction mixtures.

The selectivity of the catalyst is determined by analyzing the reactionproduct mixture and comparing the amount present of various reactionproducts. In the case of amination of ethylene glycol andmonoethanolamine to produce ethylene diamine selectivity is determinedby comparing the amount of ethylenediamine (EDA) with the amount ofpiperazine produced in a given conversion. The analysis of the reactionproduct mixture is generally done by gas chromatographic separation.Examples of columns which have been used in the gas chromatographicanalysis of such reaction mixtures include TERGITOL NP-27 on CHROMOSORBT and TERGITOL E-68 on CHROMOSORB Z. A particularly preferred columncomprises Carbowax 30M on Chromosorb 750 having a particle size of 40-60mesh and wherein the column is 8 feet long having an inner diameter of1/8 inch.

EXAMPLE 2 Comparison of Different Metals in Catalysts

This example concerns an evaluation of the activity and selectivity ofvarious catalysts identified in Table No. 2 All of the catalysts used inthis example were prepared by the same general technique.

Preparation of Impregnating Solutions

Stock solutions containing Ni, Cu, Pd, and Re were prepared bydissolving a known quantity of an appropriate metal salt in water. Themetal salts, amounts used, and the final metal concentration aretabulated below.

    ______________________________________                                        No. of                                  Gms.                                  Solu-             Mole   Gms.           Metal/                                tion  Metal Salt  Wt.    Salt Gms. H.sub.2 O                                                                          ml soln                               ______________________________________                                        1     Ni(NO.sub.3).sub.2.6H.sub.2 O                                                             290.8  66   300       .05                                   2     Pd Cl.sub.2 177.3  6.6  380 +     .009                                                                70ml conc.                                                                    HCl                                             3     Cu(NO.sub.3).sub.2.3H.sub.2 O                                                             241.6  7.6  200       .01                                   4     NH.sub.4 ReO.sub.4                                                                        268.2  8    100       .056                                  ______________________________________                                    

Preparation of Catalysts Nickel on Norton α-alumina LA-4102.

The support (19 grams) was placed in a 250 ml. round botton flask, water(25 mls) and ethanol (25 mls) were added. After swirling, 20 mls. ofsolution No. 1 was added. A solution containing ammonium carbonate (3gm) in 25 mls. of water was added dropwise to the metal-support slurry.The slurry was evaporated to dryness on a vacuum rotary evaporator. Thecoated catalyst was transferred to a porcelain evaporating dish, anddried at 120° C for two hours. The catalyst was then roasted at 300° Cfor two hours in a muffle furnace, cooled to room temperature,transferred to a quartz tube and placed in a tube furnace. The tubefurnace was heated to 300° C, and the catalyst was reduced in a streamof hydrogen gas for two hours, 40 minutes. The quartz tube was purgedwith N₂ gas while cooling to room temperature, and the catalyst wasstored under N₂ until tested.

Nickel on CXC Carbon, Nickel - JM - 408*, and Nickel-Girdler Silica,T869

These catalysts were prepared using the same procedure described for thepreparation of the Ni-α -alumina catalyst. The carbon used was NationalCarbon Company's CXC 6/8 mesh.

Nickel-Copper Catalysts

These catalysts were prepared using essentially the same procedure asdescribed above for the Ni-α -alumina catalyst. The amount of supportused was increased to 38 grams, and a 500 ml. round bottom was used.After slurrying the support with a solution containing 50 mls. H₂ O and40 mls. ethanol, 36 mls. of solution No. 1 followed by 20 mls. ofsolution No. 3 were added. This gives a Ni/Cu atom ratio ofapproximately 8.7/1. A solution containing 6 gm. of ammonium carbonatein 50 mls. of water was then added, and the resulting slurry wasevaporated to dryness using a vacuum rotary evaporator. The drying,roasting, and reduction steps were conducted as described previously.The catalysts were stored under N₂ prior to testing. The Ni-Cu catalyston CXC carbon was pyrophoric.

Ni-Pd Catalysts

These catalysts were prepared using a slight modification of theprevious procedure. The support (38 gm.) was placed in a 500 ml. roundbottom flask and 40 mls. Ethanol (200 proof) was added, followed by 32mls. of solution No. 1 and 43 mls. of solution No. 2. This gives aslurry containing a Ni/Pd atom ratio of approximately 7/1. Powderedammonium carbonate was then added portion wise until the PH of theslurry increased to approximately 8 (Hydrion paper). The slurry was thenevaporated to near dryness using a vacuum rotary evaporator. The masswas reslurried in 50 mls. of fresh absolute ethanol and evaporated todryness. The drying, roasting, and reduction steps were conducted asdescribed above.

Ni-Re Catalysts

These catalysts were prepared using the procedure described forpreparation of the Ni-Pd catalysts. Again, 38 grams of support was used,and after slurrying the supports in 50 mls. ethanol, 32 mls. of solutionNo. 1 followed by 7.2 mls. of solution No. 4 were added. This gives aNi/Re atom ratio of approximately 11.3/1. The evaporation, drying,roasting and reduction steps were as described for the Ni catalysts. Twoof the reduced Ni-Re catalysts were pyrophoric, Ni-Re on CXC Carbon andNi-Re on JM-408.

The metal loading in each case was a maximum of 5 percent by weight ofthe support, assuming that 100 percent of the available metal was pickedup by the support.

The catalysts were tested in a 0.5 liter rocker autoclave. In each case,the catalyst (5 gm.) slurried in MEA (25.5 gm., 0.42 moles), and water(5 gm., if any), was charged to the autoclave. The autoclave waspressurized with hydrogen to the required pressure (50 or 200 PSIG), andfinally liquid ammonia (71 gm., 4.17 mole) was pressured into theautoclave via a hoke cylinder. The reaction mixture was heated to therequired temperature (175 or 225) and held at reaction temperature forsix hours.

The results of the 16 tests are reported in Table 2. The analyses of theproduct was done by the techniques described in Example 1. The mostactive catalyst tested was a Nickel-Rhenium based catalyst on α-alumina(run No. 13). This catalyst also shows a high degree of selectivity(EDA/DEDA).

                                      TABLE 2                                     __________________________________________________________________________    CONVERSION OF MONOETHANOLAMINE TO ETHYLENEDIAMINE                                                                  Approx.                                                   Run H.sub.2                                                                           Ml H.sub.2 O                                                                         % H.sub.2 O                                                                        % MEA                                    Run No.                                                                            CATALYST    Temp.                                                                             PSIG                                                                              CHARGED                                                                              in Prod.                                                                           CONVERTED                                                                             Products   EDA/DEDA              __________________________________________________________________________    1    Ni on α-alumina                                                                     175 50  nil    1.6  5       EDA        ∞               2    Ni on CXC Carbon                                                                          175 200 5      1.9  6       No Products                                                                              --sd.                 3    Ni on JM-408                                                                              225 200 nil    6.4  22      EDA, DEDA  12.6                  4    Ni on Girdler Silica*                                                                     225 50  5      4.2  14      EDA, DEDA  5.5                   5    Ni-Cu on α-alumina                                                                  175 50  nil    0.9  3       EDA        ∞               6    Ni-Cu on CXC Carbon                                                                       175 200 5      3.6  12      No Products                                                                              --sd.                 7    Ni-Cu on JM-408                                                                           225 200 nil    4.0  13      EDA. DEDA  9.9                   8    Ni-Cu on Girdler Silica                                                                   225 50  5      7.7  26      EDA, DEDA  1.0                   9    Ni-Pd on α-alumina                                                                  225 200 5      4.4  15      EDA, DEDA  1.3                   10   Ni-Pd on CXC Carbon                                                                       225 50  nil    4.7  16      Trace EDA and                                                                            --ks                  11   Ni-Pd on JM-408                                                                           175 50  5      1.7  6       No Products                                                                              --sd.                 12   Ni-Pd on Girdler Silica                                                                   175 200 nil    4.3  15      EDA        ∞               13   Ni-Re on α-alumina                                                                  225 200 5      14.0 48      EDA, DEDA   4.75                 14   Ni-Re on CXC                                                                              225 50  nil    3.4  12      No Products                                                                              --sd.                 15   Ni-Re on JM-408                                                                           175 50  5      0.6  2       EDA        ∞               16   Ni-Re on Girdler Silica                                                                   175 200 nil    2.6  9       EDA        ∞               __________________________________________________________________________     *T869?                                                                   

EXAMPLE 3 Ni/Re Atom Ratio

For this example ten nickel-rhenium catalysts have been prepared on anumber of different support materials including Girdler supports T372,and T373; Davison 980-13; and Norton LA 4102.

All of these catalysts were prepared by the same general procedure. Asolution containing Ni(NO₃)₂ · 6H₂ O and NH₄ ReO₄ dissolved in 12 mls ofdistilled water was prepared.

The impregnation procedure involving adding the nickelrhenium solutionto 19 grams of dried, evacuated support material via a syringe. Theimpregnated support was dried in an oven at 120° C for several hours,and then placed in a muffle oven at a specified temperature (calciningtemperature) for 3 hrs. to calcine the catalyst. After calcining, thecatalyst was placed in a quartz tube and purged with a continuousnitrogen flow (10-20 cc/min.) while being heated to a record specifiedtemperature. Upon reaching this temperature (reduction temperature) theflow of nitrogen was interrupted and hydrogen was fed at 10-20 cc/minthrough the tube for 3 hrs. to reduce the metal oxides and activate thecatalyst. After this activation, the flow of hydrogen was interruptedand nitrogen was fed through the quartz tube and the catalyst waspermitted to cool to room temperature (25° C). The activated catalystwas stored under nitrogen until used.

The above procedure is a general one and was used to prepare the tennickel-rhenium catalysts.

The catalysts differed by the Ni/Re ratio, the calcining temperature,the reduction temperature, and the support used as shown in the Table 3.The amounts of Ni(NO₃)₂ ·6H₂ O and NH₄ ReO₄ used to prepare the abovecatalysts were varied to give in each case a catalyst containing thedesired Ni/Re atom ratio. All of the catalysts were prepared to contain5 wt. % total metal (Ni + Re) on the support.

The above catalysts were tested for activity to convert monoethanolamineto ethylenediamine using a 0.5 liter Parr rocker autoclave constructedof carpenter-20 alloy. The test procedure involved charging 5 grams ofthe appropriate catalyst, 26 gm (0.5 mole) of monoethanolamine, and 200PSIG of hydrogen to the autoclave. Next, 72 grams of anhydrous ammoniawas pressured into the autoclave, and the autoclave was heated to 200°C. The reaction temperature was maintained at 200° C for 1 hour and thenthe autoclave was allowed to cool to room temperature (˜23° C). Theexcess ammonia was slowly vented from the autoclave, and the productswere recovered essentially ammonia-free.

The crude, ammonia-free products were first analyzed for water contentusing the Karl Fisher titration method to determine the extent ofmonoethanolamine reacted.

                  TABLE 3                                                         ______________________________________                                                              Temp.                                                   Cat-                  ° C                                                                          Girdler                                           alyst                                                                              Ratio   Calcining                                                                              Reduc-                                                                              Support      EDA/                                 No.  Ni/Re   Temp. ° C                                                                       tion  Used   % H.sub.2 O                                                                         DEDA                                 ______________________________________                                        1    15/1    300      300   T869   13.5  Not run                              2    30/1    300      600   T869   5.0   5.4                                  3    15/1    300      600   T372   4.2   EDA only                             4    30/1    300      300   T372   5.7   24                                   5    15/1    600      600   T372   3.9   EDA only                             6    30/1    600      300   T372   3.3   Not run                              7    15/1    600      300   T869   10.3  7.7                                  8    30/1    600      600   T869   5.3   Not run                              9    10/1    300      300   T869   16.7  3.2                                  10   10/1    300      300   T372   7.4   Not run                              ______________________________________                                    

The data analysis of the products, namely the water content and productratio of EDA to DEDA also appears in Table No. 3. The results indicate aclear dependence of catalyst activity on Ni/Re atom ratio. The datashows that the T869 supported catalysts with a 10/1 and 15/1 Ni/Re atomratio are more active than those With a 30/1 Ni/Re atom ratio. Also, theT869 supported catalysts are more active than the T372 supportedcatalysts.

EXAMPLE 4 Varying The Ni-Re Loading

This example illustrates the effect on activity and selectivity ofvarying the total weight % of nickel-rhenium metal impregnated on thecatalyst support.

Four catalysts were prepared having different amounts of total nickeland rhenium metal on Girdler T869 and T1571 supports.

12.5% Ni-Re on Girdler T1571

A solution containing 18.8 gms. of Ni(NO₃)₂ ·6H₂ O and 1.73 gms. NH₄ReO₄ dissolved in 52 mls. of water was prepared. 35 gms. of T1571support was dried in an oven at 120° C and evacuated. 26 mls. of theabove Ni-Re solution was slurried with the dried, evacuated support. Theimpregnated support was then dried, evacuated, and impregnated with asecond 26 ml portion of the Ni-Re solution. The support was again dried,calcined, and reduced at 300° C for 3 hours in a stream of hydrogen.

30% Ni-Re on T1571 Support

A solution containing 45.12 gm Ni(NO₃)₂ ·6H₂ O and 4.12 gm of NH₄ ReO₄dissolved in 62 mls of water was prepared and used to impregnate 28grams of Girdler T1571 support. The impregnation procedure was similarto that described for the 12.5% Ni-Re catalyst except that 21 mls of theabove Ni-Re solution was used per impregnation. A total of 3impregnations were required to absorb all of the Ni-Re on the support.The impregnated support was calcined at 300° C for 3 hours, and thenreduced for 3 hours at 300° C in hydrogen.

30% Ni-Re on T869 Support

A solution prepared by dissolving 45.12 gm Ni(NO₃)₂. 6H₂ O and 4.12 gmNH₄ ReOH in 59 mls of water was used to impregnate 28 gms of GirdlerT869 support. The impregnation required 4 coatings with 15 mls of theNi-Re solution per coating. The impregnated support was calcined at 300°C for 3 hours and then reduced in a stream of hydrogen for 3 hours at300° C.

12.5% Ni-Re on T869 Support

A solution of 18.8 gm of Ni(NO₃)₂ .6H₂ O and 1.73 gm of NH₄ ReO₄ in 37mls of water was prepared, and used to impregnate 35 gms. of GirdlerT869 support. The impregnation required 2 coatings with 18.5 mls of theNi-Re solution per coating. The impregnated catalyst was calcined for 3hours at 300° C and reduced for 3 hours at 300° C.

The above four catalysts were tested for activity and selectivity in theconversion of ethylene glycol to ethylenediamine, monoethanolamine, andpiperazine in a 0.5 l Parr rocker autoclave constructed of carpenter 20alloy. The procedures used to charge the autoclave, and analyze theproducts were identical to those described in Example 2 above. Thespecific reaction conditions are set forth in the table below. Thereaction time for each experiment was 45 minutes where the reactiontimes were measured after the reaction mixture reached the desiredreaction temperature.

                                      TABLE 4                                     __________________________________________________________________________       Girdler                                                                            Weight                                                                   Catalyst                                                                           % Total                                                                             Feed Mole                                                                           Reaction                                                                           Weight                                                                              Product                                        Exp.                                                                             Support                                                                            Metal On                                                                            Ratio Temp.                                                                              % H.sub.2 O in                                                                      Ratio                                          No.                                                                              Used the Support                                                                         NH.sub.3 /EG                                                                        ° C                                                                         Product                                                                             EDA/DEA                                        __________________________________________________________________________    1  T1571                                                                              12.5  13/1  200  10.3  3.0                                            2  T869 12.5  13/1  225  30.8  0.6                                            3  T1571                                                                              30.0  13/1  225  32.2  0.7                                            4  T869 30.0  13/1  200  10.9  4.3                                            5  T1571                                                                              12.5  20/1  225  10.3  2.4                                            6  T869 12.5  20/1  200  7.3   13.0                                           7  T1571                                                                              30.0  20/1  200  9.2   10.6                                           8  T869 30.0  20/1  225  15.7  4.4                                            __________________________________________________________________________

The respective feeds of reactants in each of the experimental runs areas follows:

    ______________________________________                                                                   Gms.                                               Exp. Nos.                                                                             Gms. NH.sub.3                                                                           Gms. EG  Catalyst                                                                              Initial H.sub.2 Press                      ______________________________________                                        1,2,3,4  68.0     19.0     5.0     200 PSIG                                   5,6,7,8 104.0     19.0     5.0     200 PSIG                                   ______________________________________                                    

Analysis of the data from the eight experimental runs of Table 4 showthat the 12.5% metal catalyst supported on T869 is more active than the30% metal catalyst supported on T869. Conversely the 30% metal catalystsupported on T1571 is more active than the 12.5% metal catalystsupported on T1571. The data confirms that the degree of ethyleneglycolconversion can be increased either by increasing the reactiontemperature from 200° to 225° C, or by decreasing the NH₃ /EG feed moleratio from 20/1 to 13/1.

EXAMPLE 5 Amination Reaction Conditions

This example demonstates that Ni-Re based catalysts are active forconverting ethylene glycol to ethylene-diamine, monoethanolamine, andpiperazine. Also shown is the effect of the various reactions variableson the conversion of ethylene glycol.

A. Preparation of Catalysts

Two batches of nickel-rhenium based catalysts supported on Girdlersupports T869 and T1571 were prepared. Each of the catalyst supportswere impregnated with 5 weight % total metal (as Ni° + Re° ) having aNi/Re atom ratio of 10/1. The supports were impregnated as describedbelow.

Preparation of 5% Ni-Re on Girdler T869

A solution containing 24.7 gm of Ni (NO₃)₂.6 H₂ O and 2.278 gms. of NH₄ReO₄ in 67 mls. of water was prepared. 130 gms Girdler T869 support (1/8inch extrusions) was prepared for impregnation by drying for 3 hours ina 120° C oven, and then allowed to cool in an evacuated flask. The Ni-Resolution was added to the dried, evacuated support through an additionfunnel. After slurrying the support with the Ni-Re solution, theimpregnated support was dried at 120° C and then calcined for 3 hrs. at300° C. Finally, the catalyst was activated by reduction in a stream ofhydrogen for 3 hrs. at 300° C. After cooling to room temperature, thecatalyst was stored under nitrogen prior to testing.

Preparation of 5% Ni-Re on Girdler T1571 Support

A solution of 7.51 gms of Ni(NO₃)₂.6 H₂ O and 0.6926 gm. of NH₄ ReO₄ in29 mls of water was prepared. The slurry was warmed to dissolve thesalts. The support was prepared for impregnation by drying for 3 hrs. at120° C, and then cooled to room temperature under vacuum. The Ni-Resolution was added to the evacuated support via an addition funnel. Theimpregnated support was dried. Calcined and reduced as describedpreviously for the preparation of Ni-Re on T869 support.

B. Amination Reaction

Using the above prepared catalysts, a series of eight experimentsoutlined in the following table were conducted.

                                      Table 5                                     __________________________________________________________________________       Feed Mole       Initial                                                                             Wt. %                                                                              Product                                         Exp.                                                                             Ratio                                                                              Reaction                                                                            Catalyst                                                                           Hydrogen                                                                            H.sub.2 O in                                                                       Ratio                                           No.                                                                              NH.sub.3 /EG                                                                       Time (min.)                                                                         Support                                                                            Pressure                                                                            Product                                                                            EDA/DEDA                                        __________________________________________________________________________    1  15/1 45    T869 200   10.0 5.7                                             2  25/1 45    T869 300   8.7  10.6                                            3  15/1 90    T869 300   11.7 5.3                                             4  25/1 90    T869 200   8.6  12                                              5  15/1 45    T1571                                                                              300   3.3  Only MEA                                        6  25/1 45    T1571                                                                              200   2.5  Only MEA                                        7  15/1 90    T1571                                                                              200   7.6  7.5                                             8  25/1 90    T1571                                                                              300   5.8  12                                              __________________________________________________________________________

All of the experiments outlined in the above table were conducted in a0.5 l Parr autoclave constructed of carpenter 20 Alloy. In eachexperiment 5 grams of the specified catalyst and 18.6 grams of ethyleneglycol were charged to the autoclave. Next the autoclave was pressurizedwith hydrogen to the specified initial pressure (PSIG), and then therequired amount of ammonia was forced into the autoclave under nitrogenpressure. The amount of ammonia charged was either 76 gm or 128 gmsdepending upon the desired NH₃ /EG feed mole ratio; 76 grams was chargedfor experiments 1, 3, 5, 7 and 128 grams was charged for experiments 2,4, 6, 8.

After charging the ammonia the autoclave was heated, while being rocked,to 200° C. Upon reaching 200° C, the reaction temperature was maintainedfor the specified time, and then the autoclave heater was turned off.The autoclave was allowed to cool to room temperature, and the excessammonia was slowly vented to reduce the pressure in the autoclave toatmospheric pressure.

In Table 5 above, for each experiment, the wt. % water in the finalproduct (NH₃ -free basis) is tabulated together with the area-ratio ofEDA to DEDA obtained from gas-chromatographic analysis of the reactionmixtures. In all experiments the reaction mixtures were found to containmonoethanolamine and some unreacted ethyleneglycol. In experiments 1, 2,3, 4, 7 and 8 the reaction mixture also contained ethylenediamine andpiperazine.

The data reported in Table 5 confirms that T869 supported catalysts aremore active than the T1571 catalysts and that degree of ethylene glycolconversion increases with increasing reaction time. Also shown is thatthe selectivity to ethylenediamine decreases as the conversion ofethylene glycol increases.

The data demonstrates the effect of varying the feed mole ratio ofammonia to ethylene glycol. Increasing the NH₃ /EG feed mole ratio from15/1 to 25/1 decreased the degree of ethylene glycol conversion.However, the increase in the NH₃ /EG mole ratio increased theselectivity of the reaction to form ethylenediamine as compared with thepiperazine product.

The conversion of ethylene glycol does not appear to be effected by thehydrogen pressure within the ranges examined in these experiments

EXAMPLE 6 Ni-Re-B Catalyst

This example illustrates that a beneficial effect on activity can beobtained by adding Boron to a nickel-rhenium catalyst. This isaccomplished by adding boric acid to the Ni(NO₃)₂.6 H₂ O and NH₄ ReO₄aqueous solution used to impregnate Girdler T869 support as describedmore fully below.

A solution containing 5.13 gm Ni(NO₃)₂.6 H₂ O, 0.47 gms NH₄ ReO₄ and 1.3gm H₃ BO₃ in 19 ml of distilled water was prepared. 18 gms of predriedGirdler T869 support was placed in a 250 ml round bottom flask, and theflask was equipped with a vacuum adapter. The flask was evacuated bymeans of a vacuum pump, and then 9.5 mls of the above aqueous solutioncontaining Ni-Re and H₃ BO₃ was added to the support via a syringe. Theimpregnated support was re-dried at 120° C for 3 hours and impregnatedas described above with a second 9.5 mls of the Ni/Re/B solution. Thecompletely impregnated support was dried at 120° C for 3 hours, calcinedat 300° C in a muffle furnace for 3 hours, and finally reduced at 300° Cfor 3 hours in a stream of hydrogen.

To above catalyst was tested for activity to convert ethylene-glycol toethylene diamine, monoethanolamine and piperazine using the 0.5 l Parrautoclave described above. The experiments conducted are outlined inTable 6 below. For comparison purposes, a similar catalyst prepared onT869 support except that it contained only nickel and rhenium was testedunder the identical experimental conditions. In both experiments thereaction temperature was 200° C and the initial hydrogen pressure was200 PSIG. The data in Table 6 clearly show that nickel-rhenium-boroncontaining catalyst is more active than the nickel-rhenium catalyst

                                      TABLE 6                                     __________________________________________________________________________                                      Product                                                                 Wt. % Ratio                                       Exp.         Gms  Gms Gms                                                                              Rxn                                                                              H.sub.2 O                                                                           EDA                                         No.                                                                              Catalyst  Catalyst                                                                           NH.sub.3                                                                          EG Time                                                                             in Prod.                                                                            DEDA                                        __________________________________________________________________________    1  Ni-Re-B on T869                                                                         5    76  19 1 hr                                                                             15.7  5.5                                         2  Ni-Re on T869                                                                           5    76  19 1 hr                                                                             9.5   6.8                                         __________________________________________________________________________

EXAMPLE 7 Amination of Ethanol, 2-Propanol, and Acetone

A nickel-rhenium catalyst, further containing boron, was prepared totest its effectiveness in aminating ethanol, 2-propanol, and acetone.

A nickel-rhenium catalyst was prepared by impregnating 200 gms Girdler'sK306 support with 100 mls of an aqueous solution containing 64.5 gms ofNi(NO₃)₂.6 H₂ O, 5.95 gms of NH₄ ReO₄, and 1.37 gm of H₃ BO₃. Theimpregnated support was dried in an oven at 125° C for 3 hrs., calcinedat 300° C for 3 hrs., and finally reduced in a stream of hydrogen for 3hrs. at 300° C. The activated catalyst was stored under nitrogen untilused.

All aminations were conducted in an 0.5 l rocker autoclave constructedof stainless steel. Five grams of the Ni-Re catalyst on K306 was placedin a rocker bomb autoclave which had been flushed out with nitrogen. Thealcohol or ketone was placed in a test tube attached to a dip tube whichfitted into the bomb autoclave. The bomb was sealed and pressurized to200 psig with hydrogen. Next, the bomb was placed in the heating jacketof the rocking device, and the desired amount of liquid ammonia waspressured into the bomb via nitrogen pressurized Hoke cylinder. The NH₃-catalyst-H₂ mix was then heated to 190° C., and the rocker was switchedon. On the first down-stroke the bomb was tipped sufficiently to permitthe alcohol or ketone to dump from the test-tube, and come into contactwith the catalyst-NH₃ -H₂ mixture. The reaction timer was started atthis point. The particular reaction conditions for each of the threeaminations are summarized in the following table:

    ______________________________________                                                                              ° C.                             Run  Amination of                                                                             Gms.     Gms.  Gms.   Rxn.  Rxn.                              No.  (compound) Catalyst NH.sub.3                                                                           Compound                                                                              Temp. Time                              ______________________________________                                        1    Ethanol    5        79   21.3    190   2 hr.                             2    2-Propanol 5        39.5 27.8    190   2 hr.                             3    Acetone    5        79   27      190   2 hr.                             ______________________________________                                    

After the desired reaction time, the liquid contents of the bomb werevented into a cold trap. After warming to room temperature, samples ofthe reaction products were analyzed by gas chromatography to determinethe products of the reaction. The results obtained are tabulated below.

    ______________________________________                                                      Run 1     Run 2      Run 3                                      Products      Ethanol   2-Propanol Acetone                                    ______________________________________                                        Ammonia       4.0       5.2        1.4                                        Water         13.07     15.67      37.4                                       Ethylamine    13.82     --         --                                         Diethylamine  0.21      --         --                                         Triethylamine 0.30      --         --                                         Ethanol       68.5      --         --                                         Acetone       --        0.11       16.95                                      2-Propanol    --        51.31      12.06                                      Isopropylamine                                                                              --        27.42      28.14                                      Diisopropylamine                                                                            --        0.34       2.36                                       ______________________________________                                    

The high selectivity to the aminated products ethylamine andisopropylamine, are clear from the data. It is noted that in the case ofacetone there is a substantial mount of the intermediate 2-propanolpresent in the reaction mixture but this is an expected intermediate inthe ultimate production of the isopropylamine.

EXAMPLE 8 1,3-Propanediol Conversion

The nickel-rhenium based catalysts are also active catalysts for theconversion of higher molecular weight diols such as 1,3-propane-diol todiamines. This experiment shows that 1,3-propanediol is converted to amixture of 1,3-propanediamine and 3-hydroxypropylamine over anickel-rhenium catalyst.

A nickel-rhenium catalyst was prepared by impregnating 130 grams ofGirdler support T869 with 67 mls of an aqueous solution containing 24.7gm of Ni(NO₃)₂ .6H₂ O and 2.28 gms of NH₄ ReO₄. The impregnated catalystsupport was dried at 120° C for several hours, calcined at 300° C for 3hours, and reduced in a stream of hydrogen at 300° C for 3 hours.

Five grams of the above catalyst was charged to a 0.5 l rockerautoclave, together with 32 gm of 1,3-propanediol. The autoclave wassealed, and pressurized to 200 PSIG with hydrogen. Next, 107 gm ofanhydrous ammonia was pressured into the autoclave. The autoclave washeated to 200° C and maintained at 200° C for two hours. After coolingto room temperature the excess ammonia was vented from the autoclave,the autoclave was opened and the reaction mixture was collected.

Analysis of the reaction mixture by gas chromatography showed thatsignificant amounts of 1,3-propanediamine and 3-hydroxypropylamine wereproduced during the reaction. Analysis of the crude reaction mixture forwater content by Karl Fisher titration showed that the reaction mixturecontained 15.2 wt.% water. This amount of water indicates that about 45%of the 1,3-propanediol charged had been converted to products.

What is claimed is:
 1. A catalytic composition having high activity andselectivity in the amination of lower aliphatic alkane derivatives tothe corresponding alkylamine, said catalyst comprising rhenium, nickeland boron impregnated on a support material selected from the groupconsisting of α-aluminas, silicas, silica-aluminas, kieselguhrs,diatomaceous earth and silica-Titanias wherein the ratio of nickel toboron to rhenium is in the range of from about 2:2:1 to about 30:30:1and the total nickel, boron and rhenium present is in the range of about3 to about 30 percent by weight of the support material, wherein saidcatalyst is activated by reduction in the presence of hydrogen atelevated temperature.
 2. The composition of claim 1 wherein the supportmaterial has a surface area of at least 1 m² /gram.
 3. The compositionof claim 2 wherein the support material is a diatomaceous silica havinga surface area greater than 10 square meters per gram.
 4. Thecomposition of claim 2 wherein the support material is silica-alumina.5. The composition of claim 4 wherein the silica-alumina support has asurface area of about 60 m² /gm.
 6. The composition of claim 2 whereinthe support material is α-alumina.
 7. The composition of claim 6 whereinthe silica support has a surface area of about 130 m² /gm.
 8. Thecomposition of claim 1 wherein the support material is silica-titania.9. The composition of claim 1 wherein the atom ratio of nickel to boronto rhenium is within the range of from about 5:5:1 to about 20:20:1. 10.The composition according to claim 7 wherein the atom ratio of nickel toboron to rhenium is within the range of from about 5:5:1 to about15:5:1.
 11. The composition of claim 1 wherein the total amount ofnickel, boron and rhenium on said support material is in the range offrom about 5 to about 15 percent by weight of the support material. 12.The composition of claim 2 wherein the nickel, boron and rhenium aresubstantially on the outer surface of the support material.
 13. Thecomposition of claim 2 wherein a substantial portion of the nickel,boron and rhenium is infused or permeated into the support material. 14.The composition of claim 1 wherein cobalt is additionally present on thesupport material.
 15. A catalyst of high activity and selectivity usefulfor aminating lower aliphatic alkane derivatives to the correspondingalkyl amines, said catalyst prepared by impregnating a support materialselected from the group consisting of δ-alumina, silica, silica-alumina,kieselguhrs, diatomaceous earths and silica - titanias with nickel,rhenium and boron to form a catalyst, and activating said catalyst byheating the catalyst in the presence of hydrogen at a temperature in therange of about 200° to about 600° C. for a period of from about 45minutes about 4 hours to form an activated catalyst, wherein saidactivated catalyst contains a total nickel, rhenium and boron metalcontent in the range of from about 3 to about 30% by weight of thesupport material and the atom ratio of nickel to boron to rhenium iswithin the range of from about 5:5:1 to about 20:20:1.
 16. Thecomposition of claim 1 which is activated by heating the composition inthe presence of hydrogen at a temperature in the range 200°-600° C for aperiod of 45 minutes to 4 hours.